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Dinuclear phosphido- and arsenido-bridged early/late transition metal complexes. Efficient catalysts for ethylene polymerization

Journal of Organometallic Chemistry
Publication Date
DOI: 10.1016/0022-328x(95)06060-a
  • Early/Late Heterodinuclear Phosphido- And Arsenido-Bridged Complexes
  • Zirconocene
  • Ethylene Polymerization
  • Crystal Structure


Abstract The reaction of ( η 5-C 5H 5) 2Zr{P(SiMe 3) 2} 2 with Ni(CO) 4 yields the heterodinuclear phosphido-bridged complex ( η 5-C 5H 5)Zr{μ-P(SiMe 3) 2)} 2Ni(CO) 2 ( 1). 1 was characterised spectroscopically and by X-ray structure determination. The central four-membered ZrP 2Ni ring is slightly puckered (dihedral angle between planes ZrP 2/ NiP 2 = 1.8°). The ZrP bond lengths are equivalent (Zr-PI 2.655(l), Zr-P2 2.652(1) Å), as are the NiP bond lengths (Ni-PI 2.264(1), Ni-P2 2.266(1) Å). The long Zr…Ni distance of 3.038(1) Å indicates the absence of a metal-metal bond. The heterodinuclear phosphido- and arsenido-bridged complexes ( η 5-C 5H 5) 2Zr{μ-E(SiMe 3) 2} 2M(CO) n [ E = P; M( CO) n = Ni( CO) 2 ( 1) or Mo(CO) 4 ( 2); and E = As M( CO) n = Cr( CO) 4 ( 3)] react rapidly with methylaluminoxane, yielding catalytically active complexes which rival the known cationic systems for the polymerization of ethylene.

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